JP4088433B2 - Method for oxidizing olefins and method for producing oxygenated compounds using the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for oxidizing olefins using molecular oxygen in the presence of a specific catalyst and a method for producing oxygen-containing compounds such as epoxides, alcohols, ketones and aldehydes, which oxidize olefins by the method.
[0002]
[Prior art]
Conventionally, various methods for producing an oxygen-containing compound by oxidizing an olefin using a solid oxidation catalyst are known. Among them, for example, with respect to a method for producing epoxide, a liquid phase reaction of propylene by a TS-1 type titanosilicate catalyst or the like is known (Japanese Patent Publication No. 54-40525, Japanese Patent Publication No. 56-35941, JP-A-8-269031, JP-A-10-337473). These methods are disadvantageous in terms of production cost because they use high hydrogen peroxide or organic hydroperoxide as the oxygen source, although the conversion rate and epoxy selectivity are high.
[0003]
On the other hand, a method using air as an oxygen source is also known. For example, a method of using a metal-containing aluminophosphate as a catalyst and oxidizing air in the liquid phase with cyclohexene, styrene, etc. has been reported (Chem. Commun., 1999). , 829-830). In this method, oxygen and air, which are oxygen sources, are inexpensive, and epoxides and the like can be obtained under mild conditions of 50 ° C. In terms of stoichiometry, there is a difficulty that a carboxylic acid equivalent to or more than the product is by-produced.
[0004]
As described above, an expensive oxygen source or a method for obtaining an undesired by-product is naturally costly. There is a need for a method that can acquire only things.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and provides a method for oxidizing various olefins with molecular oxygen using a relatively inexpensive catalyst, and further, epoxide, alcohol, ketone, aldehyde, etc. It is an object of the present invention to provide a method for efficiently producing the oxygen-containing compound.
[0006]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the present inventors used an aluminophosphate containing a solid transition metal atom (excluding vanadium atoms) as a catalyst when oxidized with molecular oxygen of olefins, By reacting under specific conditions, a wide range of olefins can be oxidized. As a result, various oxygen-containing compounds can be efficiently produced, and the catalyst can be easily separated and reused from the reaction system. The headline and the present invention were completed.
[0007]
That is, the present invention is an olefin characterized by oxidizing olefins with molecular oxygen at a reaction temperature of 60 to 200 ° C. in the presence of a catalyst comprising an aluminophosphate containing a transition metal (excluding vanadium atoms). The oxidation method is provided.
[0008]
Further, the present invention provides an oxygen-containing product characterized by oxidizing olefins with molecular oxygen at a reaction temperature of 60 to 200 ° C. in the presence of a catalyst comprising an aluminophosphate containing a transition metal (excluding vanadium atoms). A method for producing a compound is provided.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the method of the present invention will be described in detail.
The olefins used in the present invention are chain olefins, cyclic olefins, aromatic ring-containing olefins or alicyclic hydrocarbon group-containing olefins.
[0010]
Among these olefins, the linear olefins may be linear or branched, and specific examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, Examples are 1-octene and the like. The cyclic olefins may have a branched chain, and specific examples thereof include cyclopentene, cyclohexene, methylcyclohexene, cyclooctene, bicyclooctene, tricycloheptene, norbornene, menthene, α- Examples include pinene. Furthermore, examples of the aromatic ring-containing olefin include indene and styrene. Furthermore, examples of alicyclic hydrocarbon group-containing olefins include vinylcyclopentane, vinylcyclohexane, vinylnorbornane and the like.
[0011]
In the reaction of the present invention, as the molecular oxygen used for oxidation, not only high-purity oxygen gas and air, but also high-purity oxygen gas and air are mixed with nitrogen, helium, argon, methane, etc. Can be illustrated.
[0012]
Furthermore, the aluminophosphate containing a transition metal atom (excluding the vanadium atom) used as a catalyst in the reaction of the present invention is one in which a part of the aluminum atoms forming the alumino salt is substituted with a transition metal atom. .
[0013]
The aluminophosphate which is the basic form of this catalyst includes an aluminophosphate mainly composed of an aluminum atom, a phosphorus atom and an oxygen atom, and an aluminoline containing a silicon atom or a magnesium atom in addition to the aluminum atom, phosphorus atom and oxygen atom. Acid salts are exemplified.
[0014]
Among these, an aluminophosphate mainly composed of an aluminum atom, a phosphorus atom and an oxygen atom is generally represented by AlPO-m (m is an integer and represents a crystal type of the compound), and includes an aluminum atom, a phosphorus atom and an oxygen atom. The ratio is approximately 1: 1: 4. An aluminophosphate containing a silicon atom or a magnesium atom in addition to an aluminum atom, a phosphorus atom and an oxygen atom is generally represented by SAPO-n or MAPO-n (n is an integer representing the crystal type of the compound), It is shown that some of the aluminum atoms are replaced by silicon atoms or magnesium atoms. And the ratio of the sum of an aluminum atom and a silicon atom or a magnesium atom in the said aluminophosphate, a phosphorus atom, and an oxygen atom is about 1: 1: 4. (For the notations such as AlPO-m, SAPO-n, and MAPO-n, see “Zeolite Science and Engineering”, pages 2 to 5 (2000, published by Kodansha).)
[0015]
As the transition metal in the aluminophosphate, a transition metal other than vanadium can be used, and preferably one or more selected from iron, cobalt, nickel, copper, manganese, chromium, and the like. Of the transition metals. More preferably, it is 1 type or 2 types chosen from iron, cobalt, copper, manganese, and chromium.
[0016]
The amount of transition metal atoms contained in the aluminophosphate is about 0.01 to 20 mol%, preferably 0.1 to 10 mol, as a ratio of the amount of transition metal atoms to the total amount of transition metal atoms and aluminum atoms. %. If the amount of transition metal atoms exceeds this upper limit, the thermal stability and crystallinity of the catalyst will deteriorate, and if it is less than this lower limit, sufficient catalytic activity cannot be obtained.
[0017]
The aluminophosphate containing a transition metal atom used in the present invention is one in which a part of the aluminum atom forming the skeleton of the basic form of aluminophosphate is substituted with a transition metal atom as described above. Therefore, the transition metal atom is clearly different from the one that is physically attached to the aluminophosphate, and it is necessary to distinguish these. For this distinction, it is necessary to confirm the presence of a transition metal element by structural analysis by X-ray diffraction and ICP emission analysis.
[0018]
The aluminophosphate containing the above transition metal atom can be produced, for example, by mixing an appropriate aluminum salt, phosphate and transition metal salt and, if necessary, silicate and magnesium salt in an appropriate ratio, and mixing this with an aluminophosphate. It is synthesized by subjecting it to a hydrothermal reaction in accordance with a conventional production method. More specifically, an aluminum salt and a transition metal salt in an amount satisfying the ratio of the transition metal atom to the aluminum atom described above are used, and phosphate and the like are added thereto. US Pat. No. 4,310,440 And US Pat. No. 4,567,029 and the like.
[0019]
The aluminophosphate containing a transition metal atom used in the present invention is a porous body and is a kind of molecular sieve. Crystal structures range from near amorphous to crystalline. Any of the aluminophosphates containing these transition metal atoms can be used as a catalyst. Among them, a porous material having a crystallinity and a pore diameter of about 0.3 to 1 nm (3 to 10 angstroms) is applicable to various olefins, catalytic activity, target product selectivity or thermal stability of the catalyst. From the viewpoint of sex.
[0020]
The oxidation reaction of the present invention can be generally carried out by a liquid phase method, batchwise (batch) or continuously. As a form of the reactor, any form such as a bubble column, a stirring type, a flow type, a stirring flow type can be adopted.
[0021]
This oxidation reaction is generally carried out at a temperature of 60 to 200 ° C, preferably 80 to 150 ° C. Although there is a difference depending on the type of olefin, if it is lower than this lower limit, sufficient activity cannot be obtained. The reaction pressure is normal pressure to 10 MPa, preferably 0.5 to 5 MPa.
[0022]
In the above oxidation reaction, olefins which are reaction raw materials can be reacted as they are, but can also be diluted with a solvent and reacted. As the solvent that can be used, a solvent that is not easily oxidized, such as benzene, is preferable.
[0023]
By the oxidation method of the present invention, epoxides from olefin compounds, or alcohol compounds, aldehyde compounds, ketone compounds, etc., in which the allylic olefin is mainly oxidized to a hydroxyl group or a carbonyl group can be produced. And the kind and composition of these products change with reaction conditions, such as the kind of raw material olefins, the kind of catalyst, temperature, and pressure.
[0024]
Since the catalyst used in this reaction is a solid, it can be easily separated by centrifugation or filtration after the reaction, and can be easily recovered and reused. Moreover, when a column type reactor is filled with a catalyst and used as a fixed bed, the catalyst packed in the column can be activated and reused by heating and burning as it is.
[0025]
【Example】
The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The unreacted raw material olefin and reaction product were identified and quantified by gas chromatography. Moreover, the conversion rate of the raw material olefin and the selectivity of a product were calculated | required with the following method.
[0026]
(1) Conversion rate of olefin The conversion rate of olefin was calculated by the following calculation method by measuring the unreacted amount of the raw material (olefin).
Conversion rate (mol%) = [(A ₁ -A ₂ ) / A ₁ ] × 100
A ₁ : Raw material amount A ₂ : Unreacted raw material amount
(2) Product selectivity The selectivity of the target product was calculated by the following calculation method.
Selectivity (mol%) = _{[B 1 / (A 1 -A 2} ) ] × 100
B ₁ : Amount of target product A ₁ : Raw material amount A ₂ : Unreacted raw material amount
Reference example 1
Preparation of catalyst (CoAlPO-11):
Add 60.6 g of ion-exchanged water to a Pyrex glass beaker, add 398.98 g of aluminum triisopropoxide while stirring, and thoroughly disperse. Thereto, 249.87 g of phosphoric acid (concentration: 85% by mass), 50.38 g of cobalt acetate dihydrate and 210.5 g of ion-exchanged water were added, and the mixture was sufficiently stirred until it became homogeneous while cooling with ice. Di-n-propylamine 104.17g was added to this, and it stirred at room temperature for 1 hour. The resulting solution was transferred into an autoclave coated with Teflon and subjected to a hydrothermal synthesis reaction at 190 ° C. for 40 hours. After the reaction, filtration and washing with water were repeated to sufficiently wash the solid content and dried at 80 ° C. for 18 hours to obtain a blue powder. The obtained powder was fired at 550 ° C. for 20 hours in an air atmosphere to obtain a green powder.
[0029]
As a result of analyzing this green powder by the X-ray diffraction method, it coincided with the diffraction pattern of AlPO-11. Further, when this powder was analyzed by ICP emission analysis, the cobalt content was 5 mol% (Co mole number / (Co mole number + Al mole number) × 100). Moreover, this powder was crystalline porous, and its pore diameter was about 0.6 nm. Hereinafter, this catalyst is denoted as CoAlPO-11.
[0030]
Reference example 2
Preparation of catalyst (CoAlPO-5):
A Pyrex glass beaker was charged with 8.29 g of phosphoric acid (85% by mass), 0.3227 g of cobalt chloride hexahydrate, and 52.11 g of ion-exchanged water, and stirred well while cooling with ice. 4.87 g of CONDEA boehmite (PURAL SCF55) was added thereto, and the mixture was sufficiently stirred with ice cooling. Then, 4.36 g of triethylamine was added, and the mixture was stirred at room temperature for 18 hours. The resulting solution was transferred into an autoclave coated with Teflon and subjected to a hydrothermal synthesis reaction at 175 ° C. for 72 hours. After the reaction, filtration and washing with water were repeated to sufficiently wash the product and dried at 80 ° C. for 18 hours to obtain a blue powder. The obtained powder was baked at 550 ° C. for 16 hours in an air atmosphere to obtain a green powder.
[0031]
As a result of analyzing this powder by the X-ray diffraction method, it coincided with the diffraction pattern of AlPO-5. Further, when this powder was analyzed by ICP emission spectrometry, the cobalt content was 6 mol% (Co mole number / (Co mole number + Al mole number) × 100). Moreover, this powder was crystalline porous, and the pore diameter was about 0.7 nm. Hereinafter, this catalyst is denoted as CoAlPO-5.
[0032]
Reference example 3
Preparation of catalyst (MnSAPO-34):
In a 1500 ml container made of Teflon, 27.3 g of phosphoric acid (85% by mass) and 56.68 g of aluminum triisopropoxide were placed and mixed for 1 hour. Next, 150 ml of methanol was added and mixed for 3 hours, and then 8.33 g of sol-like cataloid silica (30% by mass in terms of SiO 2) was added and stirred for 3 hours. Next, after adding 20.4 g of tetraethylammonium hydroxide solution (concentration: 10% by mass) and stirring for 3 hours, 3.42 g of manganese acetate tetrahydrate was added and stirred for 1 hour. The obtained solution was transferred into an autoclave and subjected to a hydrothermal synthesis reaction at 210 ° C. for 40 hours. After the reaction, filtration and washing with water were repeated to sufficiently wash the product, dried at 70 ° C. for 18 hours, and further calcined at 500 ° C. for 5 hours in an air atmosphere to obtain a pink gray powder.
[0033]
As a result of analyzing the obtained powder by an X-ray diffraction method, no peaks attributable to manganese oxide and metal manganese were confirmed, and the diffraction pattern of SAPO-34 coincided. Further, when this powder was analyzed by ICP emission spectrometry, the manganese content was 4.8 mol% (Mn mole number / (Mn mole number + Al mole number) × 100). Moreover, this powder was crystalline porous, and the pore diameter was about 0.4 nm. Hereinafter, this catalyst is denoted as MnSAPO-34.
[0034]
Reference example 4
Preparation of catalyst (CoAlPO-11A):
In order to remove cobalt present as a cation species at the ion exchange site of the catalyst (CoAlPO-11) prepared in Reference Example 1, washing with an acid was performed. That is, 37.48 g of CoAlPO-11 prepared in Reference Example 1 was added to 750 g of an aqueous ammonium nitrate solution prepared to 0.1 M, and the mixture was stirred at 60 ° C. for 18 hours. Then, it returned to room temperature and wash | cleaned solid content sufficiently with ion-exchange water. Next, the solid content was dried at 100 ° C. for 20 hours, and further calcined at 550 ° C. for 3 hours in an air atmosphere. Hereinafter, this catalyst is denoted as CoAlPO-11A.
[0035]
Example 1
100 mg of the catalyst (CoAlPO-5) prepared in Reference Example 2 and 10 g of 1-octene were placed in a 50-ml stainless steel autoclave. While heating on an oil bath, air at room temperature was supplied to 1.0 MPa, and then an oxidation reaction was performed at 130 ° C. for 5 hours with stirring.
[0036]
As a result of analysis of the reaction product, the conversion rate of 1-octene was 10.8%, and the formation of epoxide compounds, alcohol compounds, ketone compounds, etc., which are 1-octene reaction products, was observed. The product selectivities were 59.1% octene epoxide, 10.8% 3-octenol to 1-octenol and 3-octenone to 22.0% 3-octenone.
[0037]
Comparative Example 1
The oxidation reaction was performed in the same manner as in Example 1 except that the reaction temperature was lowered to 80 ° C. in Example 1. As a result of analysis, substantially no oxidation product was observed. From this result, it was shown that when the reaction temperature was lowered from 130 ° C. to 80 ° C., the reaction rate rapidly decreased.
[0038]
Example 2
The reaction was performed in the same manner as in Example 1 except that the olefin raw material was changed to cyclohexene and the reaction time was 1.5 hours. As a result of the analysis, the conversion of cyclohexene was 11.9%, and the selectivity of the product was 20.5% cyclohexene oxide, 33.3% cyclohexenol, and 40.4% cyclohexenone.
[0039]
Comparative Example 2
The oxidation reaction was carried out in the same manner as in Example 2 except that the reaction temperature was 50 ° C. and the reaction time was 5 hours. As a result of the analysis, no oxidation product was observed.
[0040]
Example 3
The oxidation reaction of cyclohexene was carried out in the same manner as in Example 2 except that the catalyst (CoAlPO-11) prepared in Reference Example 1 was used. As a result of the analysis, the conversion of cyclohexene was 15.1%, and the selectivity of the product was 16.5% cyclohexene oxide, 28.0% cyclohexenol and 50.3% cyclohexenone.
[0041]
Example 4
An oxidation reaction was performed in the same manner as in Example 2 except that the catalyst (MnSAPO-34) prepared in Reference Example 3 was used. As a result of the analysis, the conversion of cyclohexene was 13.9%, and the selectivity of the product was 15.1% cyclohexene oxide, 32.0% cyclohexenol, and 50.3% cyclohexenone.
[0042]
Example 5
A stainless steel autoclave was charged with 100 mg of the catalyst (CoAlPO-5) prepared in Reference Example 2 and 10 g of benzene as a solvent, and cooled in an ice bath. Next, after adding 5 g of propylene, room temperature air was supplied to 6.0 MPa while heating in an oil bath. Thereafter, an oxidation reaction was performed at 130 ° C. for 4 hours.
[0043]
As a result of analysis, the conversion of propylene was 6.4%, and the selectivity of the product was propylene oxide 32.2%, allyl alcohol 8.0%, acetone 4.8%, acrolein 20%, acetaldehyde 18%. there were.
[0044]
Comparative Example 3
The oxidation reaction of propylene was carried out in the same manner as in Example 5 except that 10 mg of anhydrous cobalt acetate, which is a known catalyst, was used as the catalyst. As a result of analysis, the conversion of propylene was 7.9%, and the selectivity of the product was propylene oxide 15.0%, allyl alcohol 9.7%, acetone 4.0%, acrolein 26.1%, acetaldehyde 19 It was 3%.
[0045]
Although the conversion rate of this comparative example was slightly higher than that of Example 5, the selectivity for epoxide was as low as 1/2. The catalyst is extremely difficult to recover and reuse.
[0046]
Example 6
An oxidation reaction was performed in the same manner as in Example 5 except that the catalyst (CoAlPO-11) prepared in Reference Example 1 was used. As a result of the analysis, the conversion of propylene was 5.7%, and the selectivity of the product was propylene oxide 36.0%, allyl alcohol 8.2%, acetone 2.8%, acrolein 26%, acetaldehyde 17.7. %Met.
[0047]
Example 7
An oxidation reaction was performed in the same manner as in Example 5 except that the catalyst (MnSAPO-34) prepared in Reference Example 3 was used. As a result of the analysis, the conversion of propylene was 6.3%, and the selectivity of the product was propylene oxide 20.0%, allyl alcohol 4.1%, acetone 5.2%, acrolein 48.0%, acetaldehyde 18 It was 8%.
[0048]
Example 8
The reaction was performed in the same manner as in Example 5 except that the catalyst was changed to the catalyst (CoAlPO-11A) prepared in Reference Example 4. As a result of the analysis, the conversion of propylene was 2.3%, and the selectivity of the product was propylene oxide 62.5%, allyl alcohol 3.2%, acetone 0.8%, acrolein 9.1%, acetaldehyde 13 0.0%.
[0049]
Example 9
After the oxidation reaction in Example 8, the used catalyst was recovered by filtration. The collected solid was washed once with 10 g of benzene, and then used as a catalyst, and an oxidation reaction was again performed under the same conditions as in Example 8. As a result of the analysis, the conversion of propylene was 2.2%, and the selectivity of the product was propylene oxide 62.9%, allyl alcohol 2.2%, acetone 0.6%, acrolein 11.5%, acetaldehyde 13 It was 3%.
[0050]
【The invention's effect】
According to the method of the present invention, by using a solid catalyst composed of an aluminophosphate containing a transition metal (excluding vanadium atoms), a wide range of olefins can be oxidized using an easily available oxygen source.
[0051]
By this method, various oxygen-containing compounds such as epoxides, alcohols, ketones, and aldehydes can be efficiently produced from olefins, and the catalyst can be easily separated and reused. It can be used as a method for producing an oxygen-containing compound.
more than

Claims (7)

Olefin is oxidized by molecular oxygen at a reaction temperature of 60 to 200 ° C. in the presence of a catalyst comprising an aluminophosphate containing one or more transition metals selected from iron, cobalt, copper, manganese and chromium. And a method for oxidizing olefins.   The method for oxidizing olefins according to claim 1, wherein the aluminophosphate is an aluminophosphate comprising an aluminum atom, a phosphorus atom and an oxygen atom, or a silicon atom or a magnesium atom in addition to these atoms. The method for oxidizing an olefin according to claim 1 or 2 , wherein the olefin is a chain olefin, a cyclic olefin, an aromatic ring-containing olefin or an alicyclic hydrocarbon group-containing olefin.   The oxidation method according to claim 3, wherein the olefin is an olefin selected from propylene, 1-butene, 1-hexene, 1-octene, cyclopentene and cyclohexene. Olefin is oxidized by molecular oxygen at a reaction temperature of 60 to 200 ° C. in the presence of a catalyst comprising an aluminophosphate containing one or more transition metals selected from iron, cobalt, copper, manganese and chromium. And a method for producing an oxygen-containing compound. 6. The method for producing an oxygen-containing compound according to claim 5 , wherein the aluminophosphate is an aluminophosphate comprising an aluminum atom, a phosphorus atom and an oxygen atom, or a silicon atom or a magnesium atom in addition to these atoms. The method for producing an oxygen-containing compound according to claim 5 or 6 , wherein the oxygen-containing compound is epoxide, alcohol, ketone or aldehyde.